2-Cyano­anilinium dihydrogen phosphate

Zhang, L.

doi:10.1107/S1600536809034898

organic compounds

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ISSN: 2056-9890

Volume 65| Part 10| October 2009| Page o2449

doi:10.1107/S1600536809034898

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2-Cyanoanilinium dihydrogen phosphate

Li Zhang ^a ^*

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fudavid88@yahoo.com.cn

(Received 17 August 2009; accepted 31 August 2009; online 12 September 2009)

In the cation of the title compound, C₇H₇N₂⁺·H₂PO₄⁻, the nitrile group and the benzene ring are almost coplanar (r.m.s. deviation = 0.0035 Å). The cations and anions are connected by intermolecular N—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds, together with π–π interactions [centroid–centroid distance = 3.8131 (9) Å], forming a three-dimensional network.

Related literature

For applications of metal-organic coordination compounds, see: Fu et al. (2007 ); Chen et al. (2000 ); Fu & Xiong (2008 ); Xiong et al. (1999 ); Xie et al. (2003 ); Zhang et al. (2001 ). For nitrile derivatives, see: Fu et al. (2008 ); Wang et al. 2002 .

Experimental

Crystal data

C₇H₇N₂⁺·H₂PO₄⁻
M_r = 216.13
Triclinic, $[P \overline 1]$
a = 6.1471 (12) Å
b = 9.3192 (19) Å
c = 9.3295 (19) Å
α = 117.20 (2)°
β = 93.75 (2)°
γ = 99.61 (2)°
V = 462.51 (16) Å³
Z = 2
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.94, T_max = 1.00
4831 measured reflections
2110 independent reflections
1852 reflections with I > 2σ(I)
R_int = 0.030

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.102
S = 1.08
2110 reflections
129 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.37 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯O4ⁱ	0.89	1.93	2.819 (2)	176
N1—H1C⋯O1ⁱⁱ	0.89	1.85	2.723 (2)	166
N1—H1A⋯O1ⁱⁱⁱ	0.89	1.87	2.730 (2)	161
O3—H3A⋯N2^iv	0.82	1.98	2.797 (2)	176
O2—H2A⋯O4^v	0.82	1.76	2.574 (2)	172
Symmetry codes: (i) x-1, y, z-1; (ii) -x+1, -y, -z+1; (iii) x, y, z-1; (iv) -x+2, -y, -z+1; (v) -x+2, -y+1, -z+2.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809034898/pv2201sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809034898/pv2201Isup2.hkl

checkCIF report

Comment top

The construction of metal-organic coordination compounds has attracted much attention owing to potential functions, such as permittivity, fluorescence, magnetism and optical properties (Fu et al., 2007; Chen et al., 2000; Fu & Xiong (2008); Xie et al., 2003; Zhang et al.,2001; Xiong et al., 1999). Nitrile derivatives are a class of excellent ligands for the construction of novel metal-organic frameworks. (Wang et al. 2002; Fu et al., 2008). We report here the crystal structure of the title compound, 2-cyanoanilinium dihydrogen phosphate .

In the 2-cyanoanilinium cation (Fig.1), the nitrile group and the benzene ring are almost coplanar. The nitrile group C7≡N2 bond length of 1.137 (3) Å is within the normal range.

In the crystal structure, all the amine group H atoms and H₂PO₄^- H atoms are involved in N—H···O, O—H···O and O—H···N hydrogen bonds (Table 1) with N atoms of nitrile group and O atoms of H₂PO₄^- anion. The benzene rings [Cg···Cg] of neighbouring cation systems are separated by 3.8131 (9) Å [Cg is the centroid of the benzene rings]. These hydrogen bonds and π–π interactions link the ionic units into a three-dimensional network (Fig. 2).

Related literature top

For applications of metal-organic coordination compounds, see: Fu et al. (2007); Chen et al. (2000); Fu & Xiong (2008); Xiong et al. (1999); Xie et al. (2003); Zhang et al. (2001). For nitrile derivatives, see: Fu et al. (2008); Wang et al. 2002.

Experimental top

The commercial 2-aminobenzonitrile (3 mmol, 0.55 g) and H₃PO₄ (0.5 ml) were dissolved in ethanol (20 ml). Colourless block-shaped crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation at room temperature.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. A view of the title compound with the atomic numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
	Fig. 2. The crystal packing of the title compound, viewed along the a axis showing the hydrogen bonds and the π–π interactions in the title compound. H atoms not involved in hydrogen bonding (dashed lines) have been omitted for clarity

2-Cyanoanilinium dihydrogen phosphate top

Crystal data top

C₇H₇N₂⁺·H₂PO₄⁻	Z = 2
M_r = 216.13	F(000) = 224
Triclinic, P1	D_x = 1.552 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.1471 (12) Å	Cell parameters from 1852 reflections
b = 9.3192 (19) Å	θ = 3.4–27.5°
c = 9.3295 (19) Å	µ = 0.29 mm⁻¹
α = 117.20 (2)°	T = 298 K
β = 93.75 (2)°	Block, colourless
γ = 99.61 (2)°	0.30 × 0.25 × 0.20 mm
V = 462.51 (16) Å³

Data collection top

Rigaku Mercury2 diffractometer	2110 independent reflections
Radiation source: fine-focus sealed tube	1852 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.030
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.4°
CCD profile fitting scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
T_min = 0.94, T_max = 1.00	l = −12→12
4831 measured reflections

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.040	H-atom parameters constrained
wR(F²) = 0.102	w = 1/[σ²(F_o²) + (0.0436P)² + 0.23P] where P = (F_o² + 2F_c²)/3
S = 1.08	(Δ/σ)_max < 0.001
2110 reflections	Δρ_max = 0.33 e Å⁻³
129 parameters	Δρ_min = −0.37 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.126 (9)

Crystal data top

C₇H₇N₂⁺·H₂PO₄⁻	γ = 99.61 (2)°
M_r = 216.13	V = 462.51 (16) Å³
Triclinic, P1	Z = 2
a = 6.1471 (12) Å	Mo Kα radiation
b = 9.3192 (19) Å	µ = 0.29 mm⁻¹
c = 9.3295 (19) Å	T = 298 K
α = 117.20 (2)°	0.30 × 0.25 × 0.20 mm
β = 93.75 (2)°

Data collection top

Rigaku Mercury2 diffractometer	2110 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1852 reflections with I > 2σ(I)
T_min = 0.94, T_max = 1.00	R_int = 0.030
4831 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.102	H-atom parameters constrained
S = 1.08	Δρ_max = 0.33 e Å⁻³
2110 reflections	Δρ_min = −0.37 e Å⁻³
129 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	0.3606 (3)	0.17867 (19)	0.13975 (19)	0.0252 (3)
H1A	0.4996	0.1956	0.1197	0.038*
H1B	0.2813	0.2336	0.1078	0.038*
H1C	0.2980	0.0710	0.0852	0.038*
C2	0.5068 (3)	0.1896 (2)	0.3985 (2)	0.0275 (4)
C1	0.3654 (3)	0.2371 (2)	0.3135 (2)	0.0254 (4)
N2	0.7647 (4)	−0.0074 (3)	0.2631 (3)	0.0524 (6)
C7	0.6495 (4)	0.0801 (3)	0.3194 (3)	0.0343 (5)
C3	0.5080 (4)	0.2455 (3)	0.5646 (3)	0.0381 (5)
H3	0.6040	0.2152	0.6217	0.046*
C6	0.2255 (4)	0.3362 (3)	0.3937 (3)	0.0406 (5)
H6	0.1296	0.3674	0.3374	0.049*
C5	0.2268 (5)	0.3900 (3)	0.5589 (3)	0.0524 (7)
H5	0.1312	0.4571	0.6128	0.063*
C4	0.3683 (5)	0.3452 (3)	0.6444 (3)	0.0479 (6)
H4	0.3687	0.3824	0.7554	0.057*
P1	0.87212 (8)	0.26924 (6)	0.96817 (6)	0.02198 (17)
O4	1.1050 (2)	0.36166 (16)	1.05571 (18)	0.0311 (3)
O3	0.8776 (2)	0.16546 (19)	0.77991 (17)	0.0371 (4)
H3A	0.9862	0.1229	0.7672	0.056*
O2	0.7151 (2)	0.38600 (16)	0.97509 (17)	0.0294 (3)
H2A	0.7833	0.4620	0.9628	0.044*
O1	0.7610 (2)	0.15769 (17)	1.02994 (18)	0.0334 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0267 (8)	0.0251 (8)	0.0264 (8)	0.0079 (6)	0.0025 (6)	0.0141 (6)
C2	0.0282 (10)	0.0272 (9)	0.0308 (10)	0.0111 (8)	0.0046 (8)	0.0151 (8)
C1	0.0274 (10)	0.0233 (9)	0.0269 (10)	0.0076 (7)	0.0031 (7)	0.0128 (8)
N2	0.0607 (14)	0.0626 (14)	0.0557 (13)	0.0420 (12)	0.0216 (11)	0.0354 (11)
C7	0.0382 (11)	0.0409 (12)	0.0354 (11)	0.0170 (10)	0.0054 (9)	0.0252 (10)
C3	0.0446 (13)	0.0445 (12)	0.0315 (11)	0.0167 (10)	0.0029 (9)	0.0216 (10)
C6	0.0442 (13)	0.0484 (13)	0.0360 (12)	0.0294 (11)	0.0081 (10)	0.0192 (10)
C5	0.0595 (16)	0.0646 (16)	0.0396 (13)	0.0418 (14)	0.0199 (12)	0.0194 (12)
C4	0.0612 (16)	0.0555 (15)	0.0277 (11)	0.0264 (13)	0.0098 (10)	0.0156 (10)
P1	0.0221 (3)	0.0226 (3)	0.0254 (3)	0.00653 (18)	0.00367 (18)	0.0144 (2)
O4	0.0277 (7)	0.0282 (7)	0.0405 (8)	0.0032 (6)	−0.0050 (6)	0.0213 (6)
O3	0.0372 (8)	0.0480 (9)	0.0272 (8)	0.0222 (7)	0.0062 (6)	0.0144 (7)
O2	0.0253 (7)	0.0276 (7)	0.0427 (8)	0.0101 (5)	0.0087 (6)	0.0211 (6)
O1	0.0370 (8)	0.0290 (7)	0.0422 (9)	0.0056 (6)	0.0087 (6)	0.0238 (7)

Geometric parameters (Å, º) top

N1—C1	1.452 (2)	C6—C5	1.384 (3)
N1—H1A	0.8900	C6—H6	0.9300
N1—H1B	0.8900	C5—C4	1.379 (4)
N1—H1C	0.8900	C5—H5	0.9300
C2—C3	1.390 (3)	C4—H4	0.9300
C2—C1	1.393 (3)	P1—O1	1.4972 (14)
C2—C7	1.431 (3)	P1—O4	1.5004 (15)
C1—C6	1.368 (3)	P1—O2	1.5537 (14)
N2—C7	1.137 (3)	P1—O3	1.5770 (15)
C3—C4	1.368 (3)	O3—H3A	0.8200
C3—H3	0.9300	O2—H2A	0.8200

C1—N1—H1A	109.5	C1—C6—H6	120.1
C1—N1—H1B	109.5	C5—C6—H6	120.1
H1A—N1—H1B	109.5	C4—C5—C6	120.8 (2)
C1—N1—H1C	109.5	C4—C5—H5	119.6
H1A—N1—H1C	109.5	C6—C5—H5	119.6
H1B—N1—H1C	109.5	C3—C4—C5	119.5 (2)
C3—C2—C1	119.88 (18)	C3—C4—H4	120.2
C3—C2—C7	118.03 (18)	C5—C4—H4	120.2
C1—C2—C7	122.07 (18)	O1—P1—O4	113.96 (8)
C6—C1—C2	119.67 (19)	O1—P1—O2	107.38 (8)
C6—C1—N1	119.67 (17)	O4—P1—O2	112.70 (8)
C2—C1—N1	120.64 (16)	O1—P1—O3	109.65 (9)
N2—C7—C2	176.7 (2)	O4—P1—O3	109.18 (9)
C4—C3—C2	120.2 (2)	O2—P1—O3	103.43 (8)
C4—C3—H3	119.9	P1—O3—H3A	109.5
C2—C3—H3	119.9	P1—O2—H2A	109.5
C1—C6—C5	119.9 (2)

C3—C2—C1—C6	−1.2 (3)	C2—C1—C6—C5	0.6 (4)
C7—C2—C1—C6	177.2 (2)	N1—C1—C6—C5	178.9 (2)
C3—C2—C1—N1	−179.47 (18)	C1—C6—C5—C4	0.2 (4)
C7—C2—C1—N1	−1.1 (3)	C2—C3—C4—C5	−0.2 (4)
C1—C2—C3—C4	0.9 (3)	C6—C5—C4—C3	−0.4 (4)
C7—C2—C3—C4	−177.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4ⁱ	0.89	1.93	2.819 (2)	176
N1—H1C···O1ⁱⁱ	0.89	1.85	2.723 (2)	166
N1—H1A···O1ⁱⁱⁱ	0.89	1.87	2.730 (2)	161
O3—H3A···N2^iv	0.82	1.98	2.797 (2)	176
O2—H2A···O4^v	0.82	1.76	2.574 (2)	172

Symmetry codes: (i) x−1, y, z−1; (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) −x+2, −y, −z+1; (v) −x+2, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₇H₇N₂⁺·H₂PO₄⁻
M_r	216.13
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	6.1471 (12), 9.3192 (19), 9.3295 (19)
α, β, γ (°)	117.20 (2), 93.75 (2), 99.61 (2)
V (Å³)	462.51 (16)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.29
Crystal size (mm)	0.30 × 0.25 × 0.20

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.94, 1.00
No. of measured, independent and observed [I > 2σ(I)] reflections	4831, 2110, 1852
R_int	0.030
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.102, 1.08
No. of reflections	2110
No. of parameters	129
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.37

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O4ⁱ	0.89	1.93	2.819 (2)	175.5
N1—H1C···O1ⁱⁱ	0.89	1.85	2.723 (2)	166.1
N1—H1A···O1ⁱⁱⁱ	0.89	1.87	2.730 (2)	161.3
O3—H3A···N2^iv	0.82	1.98	2.797 (2)	176.1
O2—H2A···O4^v	0.82	1.76	2.574 (2)	171.5

Symmetry codes: (i) x−1, y, z−1; (ii) −x+1, −y, −z+1; (iii) x, y, z−1; (iv) −x+2, −y, −z+1; (v) −x+2, −y+1, −z+2.

Acknowledgements

This work was supported by the Outstanding Doctoral Dissertation Fund of Southeast University.

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